Chapter 10: Spontaneity, Entropy, Free Energy

Intro
- First law of thermodynamics: energy can neither be created nor destroyed (energy
of universe is constant
- The amount of energy does not change but its new form may be less useful

10.1
- a spontaneous process occurs without intervention and may be either fast or slow
- thermodynamics cannot tell us anything about the speed of a reaction
- both exothermic and endothermic processes can be spontaneous
- a process is spontaneous if it has positive entropy(S)
- nature spontaneously proceeds towards states that have a higher probability of existing
- the more microstates that can be achieved, the higher the probability, the more
spontaneous

10.2
- isothermal process: temperature of the system and surroundings remain constant at all
times
- ΔE = 0 for any isothermal process involving an ideal gas
- so… q = -w
- one step expansion (no work): a mass is removed and the gas is allowed to expand, but
the temperature does not change and no work is done because no mass is lifted
- one step expansion: the mass is made lighter now, which means that the cylinder will
expand without removing the mass. This causes the mass to be lifted and work is
performed.
W = -PexΔV
- two step expansion: w2 = P1V1
- using an infinite number of steps, the process will approach a situation where P≈Pex (this
is called a reversible process)
|wrev| = nRT*ln(V2/V1)

- one step compression: the work is equal to P1ΔV

- can be compressed in two steps as well
-as the number of steps for compression increases, the work decreases
wrev = -qrev = -nRTln(V2/V1)
-See Table 10.3 in the text for a summary
-only when these processes are done reversibly (infinite steps) does the universe remain
the same

**in a reversible cyclic process both the system and the surroundings are returned
exactly to their original conditions. As it turns out, this process is hypothetical. On the
other hand, and irreversible process is one in which, even when the system is cycled and
thus returned to its original state, the surroundings are changed in a permanent way. All
real processes are irreversible.
10.3: The Definition of Entropy
S = kB lnΩ
KB = Boltzmann’s constant, the gas constant per molecule (R/NA)
Ω = the number of microstate corresponding to a given state (including both position and
energy)
- not very practical equation when applying it to real situations

ΔS = qrev/T
- macroscopic definition of ΔS

10.4: Entropy and Physical Changes

- how does entropy depend on temperature?
ΔST1-->T2 = nCpln(T2/T1)
ΔST1T2 = nCvln(T2/T1)
- how does entropy depend on state?
- two states coexist in equilibrium at state changes
- reversible processes can only occur at equilibrium
ΔS = qrev/T
Qrev = ΔHfusion = energy required to melt 1 mol of solid at melting point
T = melting point in K

10.5: Entropy and the Second Law of Thermodynamics

- second law of thermodynamics: in any spontaneous process there is always an
increase in the entropy of the universe (the entropy of the universe is increasing)
ΔSuniv = ΔSsys + ΔSsurr
- when ΔSuniv is positive the system is spontaneous

10.6: The Effect of Temperature on Spontaneity

- entropy changes in surroundings are primarily determined by heat flow
(1) The sign of ΔSsurr depends on the direction of the heat flow. Exothermic processes
increase the entropy of the surroundings. A system tries to achieve the lowest possible
energy, so it will often transfer energy in the form of heat to the surroundings
(2) The magnitude of ΔSsurr depends on the temperature. A much greater percentage
change occurs at low temperatures
ΔSsurr = -ΔH/T (at constant temperature and pressure)

10.7: Free Energy

- free energy (G)
G = H – TS
-where H is enthalpy, T is kelvin temperature, and S is entropy
ΔG = ΔH – TΔS (at constant temperature)
ΔSuniv = -ΔG/T
-ΔG must be negative for the reaction to be spontaneous

10.8: Entropy Changes in Chemical Reactions

- if there are more gaseous reactant molecules then the entropy has increased
- third law of thermodynamics: the entropy of a perfect crystal at 0 K is zero
ΔS°reaction = ΣS°products - ΣS°reactants
- generally, the more complex the molecule, the higher the standard entropy value

10.9: Free Energy and Chemical Reactions

- the standard free energy change is represented as ΔG° and corresponds to the change in
free energy of a reaction at 25° C and 1 atm
- can also be calculated using Hess’s Law because it is a state function
ΔG° = ΣΔG°f (products) - ΣΔG°f (reactants)

10.10: The Dependence of Free Energy on Pressure

ΔG = ΔG° + RT ln(Q)
- where Q is the reaction quotient
- the system will spontaneously go to the equilibrium position, where energy is lowest

10.11: Free Energy and Equilibrium

ΔG° = -RT ln(K)
Ln(k) = -ΔH°/RT + ΔS°/R (where slope = -ΔH°/R)
Van’t Hoff equation: ln(K2/K1) = -ΔH°/R[1/T2 – 1/T1]

10.12: Free Energy and Work

wmax useful = ΔG
qp = ΔH if wuseful = 0
qp = TΔS if wuseful = wmax useful

HOMEWORK: 7, 8, 9, 13, 20, 24, 27, 30, 33, 38, 40, 45, 47, 51, 54, 59, 60, 67, 68, 70,
74, 75, 77, 84, 103, 107, 115, 119, 126